CA1277242C - Compressed powder formulation containing organophilic clay and a processfor making the formulation - Google Patents
Compressed powder formulation containing organophilic clay and a processfor making the formulationInfo
- Publication number
- CA1277242C CA1277242C CA000504475A CA504475A CA1277242C CA 1277242 C CA1277242 C CA 1277242C CA 000504475 A CA000504475 A CA 000504475A CA 504475 A CA504475 A CA 504475A CA 1277242 C CA1277242 C CA 1277242C
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- Prior art keywords
- formulation
- compressed powder
- powder formulation
- agent
- payout
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/05—Stick
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Cosmetics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Medicinal Preparation (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A compressed powder formulation which consists essentially of an organophilic clay and at least one topical agent, The formulation maintains its physical integrity upon handling thereby permitting the preparation of the formulation in the form of self-supporting sticks and exhibits an acceptable level of payout. Additionally, the formulation retains an acceptable level of payout even when contacted with water. A
process of making the formulation by compressing a powderous mixture is also set forth.
A compressed powder formulation which consists essentially of an organophilic clay and at least one topical agent, The formulation maintains its physical integrity upon handling thereby permitting the preparation of the formulation in the form of self-supporting sticks and exhibits an acceptable level of payout. Additionally, the formulation retains an acceptable level of payout even when contacted with water. A
process of making the formulation by compressing a powderous mixture is also set forth.
Description
~2~72~
BACKGROUND OF THE INVENTION
1. Field of the Invention . .
The present invention relates to a compressed powder formulation containing a substantial amount of at least one organophilic clay. The present invention also relates to a process for making the form~lation.
BACKGROUND OF THE INVENTION
1. Field of the Invention . .
The present invention relates to a compressed powder formulation containing a substantial amount of at least one organophilic clay. The present invention also relates to a process for making the form~lation.
2. Description of the Prior_Art Known antiperspirant solid formulations basically fall into four categories, namely suspensoid sticks, wax-based sticks, gelled sticks and pressed powder sticks. However, each of these types of sticks possesses certain disadvantages. A typical suspensoid or suspension stick is described in U.S. Patent No.
4,12~,679 and consists of a powdered antiperspirant active ingredient suspended in a base consisting of a fatty alcohol and a liquid siloxane. To prepare the base, the ingredients are heated to a critical temperature range, cooled at a critical rate and poured at a temperature just above the congealing point of the mass. Once the stick is cast, it will very often have voids in the middle caused by uneven cooling rates within the stick.
Further processing is needed to eliminate the voids. As should be apparent from this process description, the currently marketed suspensoid sticks are both energy and time intensive.
A further type of suspensoid stick is disclosed in U.S.
Patent No. 4,440,742. The stick consists essentially of an alkali metal bicarbonate and an optional suspending agent which is dispersed in a soap which comprises a polyhydric alcohol, alone or with a monohydric alcohol, which is gelled with an ~2~24Z
alkali metal salt of a fatty acid. The suspending agent can be colloidal or pyrogenic silica, colloidal alumina, hydrophobically treated clays or colloidal magnesium aluminum silicates.
As their name indicates, wax-based sticks contain a substantial amount of wax and therefore exhibit several inherent disadvantages. The first is the difficulty of washing the wax residue left on the clothes which can cause discoloration. The second disadvantage has to do with the naturally hydrophobic character of the waxes. That is, since the commonly used active ingredients must go into solution before they exert their effects, the wax-coating of the powered antiperspirant or deodorant ingredients inhibits the perspiration from dissolving such ingredients, This naturally decreases the efficiency of the wax-based sticks.
The gelled sticks, such as based on sodium stearate as set forth in U.S. Patent No. 4,322,400 or based on dibenzaldehyde-monosorbitol acetal as set forth in U.S. Patent No. 4,154,816, often suffer from a stability problem when used in combination with an antiperspirant agent. The acidity of common antiperspirant agents exemplified by aluminum chlorohydrate and aluminum zirconium compounds tend to break down the sodium stearate gel structure or the dibenzaldehyde thereby dele-teriously affecting the performance of the stick. In an attempt to alleviate the problem, a complexed structure of aluminum chlorohydrate and sodium chlorhydroxy lactate has been tradi-tionally used with a sodium stearate gel, but since the compound has been rendered basic due to the sodium lactate association, it loses a signifi.cant portion of its antiper~pirant activity.
~2772~Z
Attempts have also been made in the past to provide dry, pressed powder sticks useful in the cosmetics and toiletries market. These efforts have been focused in basically two directions, the withdrawal of the processing solvents after preparation and direct-compression. The withdrawal or evapo-ration of the solvents after stick formation as described in U.S.
Patent No. 4,414,200 is still energy or time consuming because a suspensoid stick must still be formed before the additional process step of evaporation.
Traditional direct-compression sticks, because of the hydrophillic character of the bases used, tend to absorb water from the air or moist environments like a bathroom or human axilla. This water both swells the base, causing it to expand and crack, and partially solubolizes any powdered active ingredients, causing a glazing of the stick surface. This glaze reduces or eliminates the payout property of the stick, largely rendering it ineffective.
It is accordingly a general object of the present invention to provide a compressed powder formulation which alleviates many of the problems of the prior art.
It is a more specific object of the present invention to provide a compressed powder formulation with an acceptable payout.
It is a further object of the present invention to provide a compressed powder formulation which maintains a substantially constant payout even after being exposed to moisture.
~27724~
It is a still further object of the present invention to provide a process of preparing a compressed powder formulation which process is efficient and results in an acceptable product.
In one aspect, the present invention provides a compressed powder formulation consisting essentially of:
a) from about 10 to about 99,95~ by weight of an organophilic clay; and b) from about 0.05 to about 90% by weight of at least one topical agent wherein the compressed powder formulation maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90~ of its original payout after being contacted with water.
In another aspect~ the present invention provides a process for making a compressed powder formulation. The process comprises:
a) mixing from about 10 to about 99.95~ by weight of an organophilic clay and from about 0.05 to about 90% of at least one topical agent to obtain a substantially uniform powderous mixture, and b) compressing the powderous mixture at a pressure in the range of from about 200 to about 1600 pounds per square inch to obtain a compressed powder formulation which maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90~ of its original payout after being contacted with water.
DE',CRIPTION OF THE PREFERRED EMBODIMENTS
As stated hereinabove, one aspect of the present invention relates to a compress~d powder formulation. The 3LZ7~24Z
compressed powder formulation consists essentially of from about 10 to about 99.95% by weight, preferably from about 40 to 80~ by weight of organophilic clay and from about 0.05 to about 90% by weight, preferably from about ?0 to about 60~ by weight of at least one topical agent.
The organophilic clay used in the present invention may be selected from those organophilic clays well known in the art including those which are commercially available. In particular, the organophilic clay may be the reaction product of a smectite-type clay having a cationic exchange capacity of at about least 75 milliequivalents per 100 grams of clay and at least one organic cation as will be defined below. Illustrative commercially available organophilic clays are illustrated by those available from NL Chemicals, Inc. of Hightstown, N.J. under the trademark "Bentone".
The smectite-type clays are well known in the art and are available from a variety of sources. The clays are preferably converted to the sodium form if they are not already in this form.
This can conveniently be done by preparing an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form. Alternatively, the clay can be mixed with water and a soluble sodium compound such as sodium carb~onate, sodium hydroxide, etc., and shearing the mixture such as with a pugmill or extruder.
Smectite clays prepared synthetically by either a pneumatolytic or, preferably, a hydrothermal synthesis process can also be used to prepare these novel organic clay complexes.
Representative of such clays are the following:
1~772~2 Montmorillonite [(Al4 XM9x)si8o2o(OH)4_fFf]
where 0.55 _ x _ 1.10, f _4 and R is selected from the group consisting of Na, Li, NH4, and m:ixtures thereof;
Bentonite [( 4-xM9x)(si8-yAly)o2o(OH)4 fFf](x+y)R+
where 0 'x '1.10, 0 ~y <1.10, 0.55 _ (x+y)_ 1.10, f~4 and R is selected from the group consisting of Na, Li, NH4 and mixtures thereof;
Beidellite [(~14+y)(Sig_x_yAlx+y)o2o(oH)4-f f]
where 0.55 _ x _ 1.10, 0_ y_ 0.44, f_ 4 and R is selected from the group consisting of Na, Li, NH4 and mixtures thereof;
Hector.ite [(M96-xLix)si~?0(oH)4-fpf~
where 0.57_ x_ 1.15, f~4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof;
4,12~,679 and consists of a powdered antiperspirant active ingredient suspended in a base consisting of a fatty alcohol and a liquid siloxane. To prepare the base, the ingredients are heated to a critical temperature range, cooled at a critical rate and poured at a temperature just above the congealing point of the mass. Once the stick is cast, it will very often have voids in the middle caused by uneven cooling rates within the stick.
Further processing is needed to eliminate the voids. As should be apparent from this process description, the currently marketed suspensoid sticks are both energy and time intensive.
A further type of suspensoid stick is disclosed in U.S.
Patent No. 4,440,742. The stick consists essentially of an alkali metal bicarbonate and an optional suspending agent which is dispersed in a soap which comprises a polyhydric alcohol, alone or with a monohydric alcohol, which is gelled with an ~2~24Z
alkali metal salt of a fatty acid. The suspending agent can be colloidal or pyrogenic silica, colloidal alumina, hydrophobically treated clays or colloidal magnesium aluminum silicates.
As their name indicates, wax-based sticks contain a substantial amount of wax and therefore exhibit several inherent disadvantages. The first is the difficulty of washing the wax residue left on the clothes which can cause discoloration. The second disadvantage has to do with the naturally hydrophobic character of the waxes. That is, since the commonly used active ingredients must go into solution before they exert their effects, the wax-coating of the powered antiperspirant or deodorant ingredients inhibits the perspiration from dissolving such ingredients, This naturally decreases the efficiency of the wax-based sticks.
The gelled sticks, such as based on sodium stearate as set forth in U.S. Patent No. 4,322,400 or based on dibenzaldehyde-monosorbitol acetal as set forth in U.S. Patent No. 4,154,816, often suffer from a stability problem when used in combination with an antiperspirant agent. The acidity of common antiperspirant agents exemplified by aluminum chlorohydrate and aluminum zirconium compounds tend to break down the sodium stearate gel structure or the dibenzaldehyde thereby dele-teriously affecting the performance of the stick. In an attempt to alleviate the problem, a complexed structure of aluminum chlorohydrate and sodium chlorhydroxy lactate has been tradi-tionally used with a sodium stearate gel, but since the compound has been rendered basic due to the sodium lactate association, it loses a signifi.cant portion of its antiper~pirant activity.
~2772~Z
Attempts have also been made in the past to provide dry, pressed powder sticks useful in the cosmetics and toiletries market. These efforts have been focused in basically two directions, the withdrawal of the processing solvents after preparation and direct-compression. The withdrawal or evapo-ration of the solvents after stick formation as described in U.S.
Patent No. 4,414,200 is still energy or time consuming because a suspensoid stick must still be formed before the additional process step of evaporation.
Traditional direct-compression sticks, because of the hydrophillic character of the bases used, tend to absorb water from the air or moist environments like a bathroom or human axilla. This water both swells the base, causing it to expand and crack, and partially solubolizes any powdered active ingredients, causing a glazing of the stick surface. This glaze reduces or eliminates the payout property of the stick, largely rendering it ineffective.
It is accordingly a general object of the present invention to provide a compressed powder formulation which alleviates many of the problems of the prior art.
It is a more specific object of the present invention to provide a compressed powder formulation with an acceptable payout.
It is a further object of the present invention to provide a compressed powder formulation which maintains a substantially constant payout even after being exposed to moisture.
~27724~
It is a still further object of the present invention to provide a process of preparing a compressed powder formulation which process is efficient and results in an acceptable product.
In one aspect, the present invention provides a compressed powder formulation consisting essentially of:
a) from about 10 to about 99,95~ by weight of an organophilic clay; and b) from about 0.05 to about 90% by weight of at least one topical agent wherein the compressed powder formulation maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90~ of its original payout after being contacted with water.
In another aspect~ the present invention provides a process for making a compressed powder formulation. The process comprises:
a) mixing from about 10 to about 99.95~ by weight of an organophilic clay and from about 0.05 to about 90% of at least one topical agent to obtain a substantially uniform powderous mixture, and b) compressing the powderous mixture at a pressure in the range of from about 200 to about 1600 pounds per square inch to obtain a compressed powder formulation which maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90~ of its original payout after being contacted with water.
DE',CRIPTION OF THE PREFERRED EMBODIMENTS
As stated hereinabove, one aspect of the present invention relates to a compress~d powder formulation. The 3LZ7~24Z
compressed powder formulation consists essentially of from about 10 to about 99.95% by weight, preferably from about 40 to 80~ by weight of organophilic clay and from about 0.05 to about 90% by weight, preferably from about ?0 to about 60~ by weight of at least one topical agent.
The organophilic clay used in the present invention may be selected from those organophilic clays well known in the art including those which are commercially available. In particular, the organophilic clay may be the reaction product of a smectite-type clay having a cationic exchange capacity of at about least 75 milliequivalents per 100 grams of clay and at least one organic cation as will be defined below. Illustrative commercially available organophilic clays are illustrated by those available from NL Chemicals, Inc. of Hightstown, N.J. under the trademark "Bentone".
The smectite-type clays are well known in the art and are available from a variety of sources. The clays are preferably converted to the sodium form if they are not already in this form.
This can conveniently be done by preparing an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form. Alternatively, the clay can be mixed with water and a soluble sodium compound such as sodium carb~onate, sodium hydroxide, etc., and shearing the mixture such as with a pugmill or extruder.
Smectite clays prepared synthetically by either a pneumatolytic or, preferably, a hydrothermal synthesis process can also be used to prepare these novel organic clay complexes.
Representative of such clays are the following:
1~772~2 Montmorillonite [(Al4 XM9x)si8o2o(OH)4_fFf]
where 0.55 _ x _ 1.10, f _4 and R is selected from the group consisting of Na, Li, NH4, and m:ixtures thereof;
Bentonite [( 4-xM9x)(si8-yAly)o2o(OH)4 fFf](x+y)R+
where 0 'x '1.10, 0 ~y <1.10, 0.55 _ (x+y)_ 1.10, f~4 and R is selected from the group consisting of Na, Li, NH4 and mixtures thereof;
Beidellite [(~14+y)(Sig_x_yAlx+y)o2o(oH)4-f f]
where 0.55 _ x _ 1.10, 0_ y_ 0.44, f_ 4 and R is selected from the group consisting of Na, Li, NH4 and mixtures thereof;
Hector.ite [(M96-xLix)si~?0(oH)4-fpf~
where 0.57_ x_ 1.15, f~4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof;
3~277~a~2 Saponite [(M96 yAly)(Si8-x-yAlx+Y)O20(OH)4-f f]
where 0.58 -x -1~18, 0 -y - 0.66, f - 4 and R is selected from the group consisting oE Na, Li, NH4, and mixtures thereof;
Stevensite - [( 96-x)sigo2o(oH)4-f~Ff]2xR~
where 0.28 'x '0.57, f = 4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof.
These clays may be synthesiæed hydrothermally by forming an aqueous reaction mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as the case may be, sodium (or alternate exchangeable cation or mixture thereof) fluoride in the proportions defined by the above formulas and the preselected values of x, y and f for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approximately 100 to 325~C., preferably 275 to 300C., for a suf~icient period of time to form the desired product.
Formulation times of 3 to 48 hours are typical at 300C.
depending on the particular smectite-type clay being synthesized, and the optimum time can readily be determined by pilot trials.
Representative hydrothermal processes for preparing synthetic smectite clays are described in U.S. Patent Nos. 3,252,757 "
~ IL277X~X
~,586,478, 3,666,407, 3,671,190, 3,844,g78, 3,844,979, 3,852,405 and 3,855,147.
The cation exchange capacity of the smectite clay can be determined by the well-known ammonium acetate method.
The organic cation which is reacted with this smectite-type clay is preferably an ammonium cation which contains at least one lineal or branched, saturated or unsaturated alkyl ~roup having 12 to 22 carbon atoms. The remaining groups of the ammonium cation are chosen from (a) lineal or branched alkyl groups having 1 to 22 carbon atoms; (b) aralkyl groups which are ben~yl and substituted benzyl moieties including fused ring moieties having lineal or branched 1 to 22 carbon atoms in the alkyl portion of the structure; (c) aryl groups such as phenyl and substituted phenyl including fused ring aromatic substituents; (d) beta, gamma, unsaturated groups having six or less carbon atoms or hydroxyalkyl groups having two to six carbon atoms; and (e) hydrogen.
The long chain alkyl radicals may be derived from natural occurring oils including various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils or fats such as tallow oil. The alkyl radicals may likewise be petrochemically derived such as from alpha olefins.
Representative examples of useful branched, satura~ed radicals include 12-methylstearyl; and 12-ethylstearyl.
Representative examples of useful branched, unsaturated radicals include 12-methyloleyl and 12-ethyloleyl. Representative examples of unbranched satura~ed radicals include lauryl;
stearyl; tridecyl; myristyl (tetradecyl); pentadecyl; hexadecyl;
. ~ i. ., ~, 12772a~2 hydrogenated tallow, docosonyl. Representative examples of unbranched, unsaturated and unsubstituted radicals include oleyl, linoleyl, linolenyl, soya and tallow.
Additional examples of aralkyl, that is benzyl and substituted benzyl moieties would include those materials derived from, e.g. benzyl halides, ben~hydryl halides, trityl halides, ~-halo- ~-phenylalkanes wherein the alkyl chain has from 1 to 22 carbon atoms such as l-halo-l-phenylethane, l-halo~l-phenyl propane, and l-halo-l-phenyloctadecane; substltuted benzyl moieties such as would be derived from ortho, meta and parachlorobenzyl halides, para-methoxybenzyl halides, ortho, meta and para-nitrilobenzyl halides, and ortho, meta and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 22 carbon atoms; and fused ring benzyl-type moieties such as would be derived from 2-halomethylnaphthalene, 9-halomethylanthracene and 9-halomethylphenanthrene, wherein the halo group would be definea as chloro, bromo, iodo, or any other such group which serves as a leaving group in the nucleophilic attack or the benzyl type moiety such that the nucleophile replaces the leaving group on the ben~yl type moiety.
Examples of aryl groups would include phenyl such as in N-alkyl and N,N-dialkyl anilines, wherein the alkyl groups contain between 1 and 22 carbon atoms; ortho, meta and para-nit.rophenyl, ortho, metal and para-alkyl phenyl, wherein the alkyl group contains between 1 and 22 carbon atoms, 2-, 3-, and 4-halophenyl ~herein the halo group is defined as chloro, bromo, : or iodo, and 2-, 3-, and 4-carboxyphenyl and esters thereof, where the alcohol of the ester is derived from an alkyl alcohol, wherein the alkyl group contains between 1 and 22 carbon atoms, _g_ ~.2'77Z4~:
aryl such as a phenol, or aralkyl such as benzyl alcohols; fused ring aryl moieties such as naphthalene, anthracene, and phenarthene.
The ~,y -unsaturated alkyl group may be selected from a wide range of materials. These compounds may be cyclic or acyclic, unsubstituted or substituted with aliphatic radicals containing up to 3 carbon atoms such that the total number of aliphatic carbons in the ~,Y-unsaturated radical is 6 or less.
The ~ unsaturated alkyl radical may be substituted with an aromatic ring that likewise is conjugated with Ithe unsaturation of the ~,y moiety or the ~,y-radical is substituted with both aliphatic radicals and aromatic rings.
Representative examples of cyclic ~,y -unsaturated alkyl ~roups include 2-cyclohexenyl and 2-cyclopentenyl.
Representative examples of acyclic ~,y -unsaturated alkyl groups containing 6 or less carbon atoms include propargyl; allyl(2-propenyl); crotyl(2~butenyl); 2-pentenyl 2-hexenyl; 3-methyl-2-butenyl; 3-methyl-2-pentenyl; 2,3-dimethyl-2-butenyl; 1,1-dimethyl-2-propenyl; 1,2-dimethyl propenyl; 2,4-pentadienyl; and 2,4-hexadienyl. Representative examples of acyclic-aromatic substituted compounds include cinnamyl(3-phenyl-2-propenyl);
2-phenyl-2-propenyl; and 3-(4 methoxyphenyl)-2-propenyl.
Representative examples of aromatic and aliphatic substituted materials include 3-phenyl-2-cyclohexenyl; 3 phenyl-2-cyclopentenyl; l,l-dimethyl-3-phenyl-2-propenyl; 1,1,2-trimethyl-3-phenyl-2-propenyl; 2,3-dimethyl-3-phenyl-2-propenyl; 3,3-dimethyl-2-phenyl-2-propenyl and 3-phenyl-2-butenyl.
The hydroxyalkyl group is selected from a hydroxyl substituted aliphatic radical wherein the hydroxyl is not ~L27~42 substituted at the carbon adjacent to the positively charged atom, and the group has from 2 to 6 aliphatic carbons. The alkyl group may be substituted with an aromatic ring independently from the 2 to 6 aliphatic carbons. Representative examples include 2-hydroxyethyl (ethanol); 3~hydroxypropyl; 4-hydroxypentyl; 6-hydroxyhexyl; 2-hydroxypropyl (isopropanol); 2-hydroxybutyl; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclohexyl; 3-hydroxy-cyclohexyl; 4-hydroxycyclohexyl; 2-hyclroxycyclopentyl; 3-hydroxycyclopentyl; 2-methyl-2-hydroxypropyl; 1,1,2-trimethyl-2-hydroxypropyl; 2-phenyl-2-hydroxyethyl; 3-methyl-2-h~droxybutyl;
and S-hydroxy-2 pentenyl.
The organic cation can thus be considered as having the following formula:
r 1 1 1 ~2 - I - R4 wherein Rl is the long chain alkyl group and R2, R3 and R4 are representative of the other possible groups described above.
The preferred organic cation is where Rl is hydrogenated tallow, R2 is benzyl and R3 and R4 are methyl.
Organophilic clay prepared from this organic cation is more fully described in U.S. Patent 4,116,866 which is commercially available from NL Chemicals, Inc.
under the trademark Bentone 27.
The amount of organic cation reacted with the smectite-type clay depends upon the specific clay and the desired degree of hydrophobicity. Typically, the amount of cation ranges from .f~ ' about 90 to about 150, preferably from about 95 to about 120 milliequivalents per 100 grams of clay, 100~ active basis.
The anion which will normally accompany the organic cation is typically one which will not adversely affect the reaction product or the recovery of the same. Such anions may be exemplified by chloride, bromide, iodide, hydroxyl, nitrite and acetate in amounts sufficient to neutralize the organic cation.
The preparation of the organic cationic salt (i.e., the organic cation paired with the anion) and the organophilic clay can be achieved by techniques well known in the!art. For example, when preparing a quaternary ammonium salt, one skilled in the art would prepare a dialkyl secondary amine, for example, by the hydrogenation of nitriles, see u.S. Patent No. 2,355,356, and then form the methyl dialkyl tertiary amine by reductive alkylation using formaldehyde as a source of the ~ethyl radical. According to procedures set forth in U.S. Patent No.
3,136,819 and U.S. Patent No. 2,775,617, quaternary amine halide may then be formed by adding benzyl chloeide or benzyl bromide to the tertiary amine. The contents of these three patents are 20 hereby incorporated by reference. As is well known in the art, the reaction with benzyl chloride or benzyl bromide can be completed by adding a minor amount of methylene chloride to the reaction mixture so that a blend of products which are predominantly benzyl substituted is obtained. This blend may then be used without further separation o~ components to prepare the organophilic clay.
The organophilic clays can be prepared by admixing the clay, the organic cationic salt and water together, preferably at a temperature within the range from about 20 to about lOO~C., ar~d pre~erably from about 35 to about 77C. for a period of time sufficient for the organic compound to coat the clay particles.
Thereafter, the organophilic clay can be subjected to a variety of optional recovery steps such as filtering, washing, drying and grinding.
Illustrative of the numerous patents which describe organic cationic salts, their manner o,E preparation and their use in the preparation of organophilic clays are commonly assigned United States Patent Nos. 2,96S,506, 4,105,578, 4,116,866, 4,208,218, 4,391,637, 4,434,076 and 4,450,095.
The organophilic clay used in the present invention may also be the reaction product of the smectite-type clay, the organic cation and an organic anion. The organic anion is selected from a wide range o materials which are capable of reacting with the organic cation in order to form an organic cation/organic anion complex which may be intercalated with the smectite-type clay. The molecular weight (gram molecular weight) of the organic anion is preferably 3,000 or less, and most preferably 1,000 or less and contains at least one acidic moiety per molecule so as to permit the formation of the organic cation/organic anion complex. The organic anion is preferably derived from an organic compound having a pKA less than about 11Ø
Preferable organic anions are derived from carboxylic acid, such as benzoic acid, sulfonic acids and alkyl sulfates, such as the lauryl half ester of sulfuric acid.
The organic anion, which includes mixtures of organic anions, is reacted with the organic cation and smectite-type clay ~ ,,27t~2~2 o form the organophilic clay and may be added to the reaction mixture in acid or salt form. Exemplary of the latter form are alkali metal salts, alkaline earth salts, ammonia and organic amines.
The amount of organic anion eeacted with smectite-type clay and the organic cation typically ranges from about 5 to about 100 milliequivalents, preferab.ly from about 10 to about 50 milliequivalents per 100 grams of clay, 100% active basis.
Illustrative patents which describe suitable organic anions which may be co-reacted with the organic cation and the smectite-type clay in order to form the organophilic clay include commonly assigned U.S. Patent Nos. 4,412,018 and 4,434,075.
The topical agent used in the compressed powder formulation may be any one or combination of materials commonly applied to a surface, especially the surface of skin. Exemplary topical agents are antiperspirant agents, deodorant agents, pigments, antifungal agents and insect repellants. The formulation may also include conventional fillers and/or processing aids, such as lubricating a~ents. Of course, the specific ingredient or ingredients used in the compressed powder formulation are selected depending upon the desired end use of the formulation. For example, when the compressed powder formulation is designed to have antiperspirant characteristics, the formulation may contain from about 10 to about 30%, preferably about 15 to about 25% by weight of known antiperspirant agents such as aluminum, chlorohydrate, aluminum chlorohydrex, aluminum zirconium chlorohydrate, aluminum ~;2772~Z
zirconium chlorohydrex, aluminum zirconium glycine complexes and mixtures thereof. The preferred antiperspirant agent is aluminum chlorohydrate.
The deodorant agent may be used alone or in combination with the antiperspirant agent and may be present in an amount ranging from about 0.05 to about 10~, preferably from about 0.1 to about 1% by weight. Typical deodorant agents include benzethonium chloride, triclosan, aluminum chlorohydrate, aluminum zirconium chlorohydrate, sodium aluminum chlorhydroxy lactate, cetyl pyridinium chloride, fragrances which will mask odors and mixtures thereof. The preferred deodorant agents are benzethonium chloride and triclosan.
Pigments which may be present in the compressed powder formulation may be any of those known in the art which do not substantially adversely affect the desired characteristics of the formulation. Fxemplary pigments are ultramarine blue, chromium oxide green, black iron oxides, titanium dioxides and mixtures thereof. When present, the amount of pigment is from about 0.5 to about 30%, preferably from about 3 to about 15% by weight.
Antifungal agent may be present in the compressed powder formulation in an amount ranging from about 1 to about 10%, preferably from about 3 to about 5~ by weight. Exemplary antifungal agents include zinc undecylenate, undecylenic acid and mixt~ures thereof. The preferred antifungal agent is a mixture of ~inc undecylenate and undecylenic acid.
Filler may be present in the compressed powder formulation in order to dilute the concentration of the active ingredients or reduce the cost. Typical fillers include talc, dicalcium phosphate, hydrophobic starch, microcrystalline ~77Z42 cellulose and mixtures thereof with the preferred filler being talc. When present, the amount of filler is fro~ about 5 to about 60~, preferably from about 20 to about 40% by weight.
A lubricating agent is used in the compressed powder formulation for the purpose of facilitating the release of the formulation from the compression mold. Typical lubricating agents include magnesium stearate, stearic acid, zinc stearate, calcium stearate and mixtures thereof with the preferred lubricating agent being magnesium stearate. When present, the amount of lubricating agent is from about 0.5 to about 3%r preferably from about 1 to about 2~ by weight.
The compressed powder formulation may be prepared by mixing the organophilic clay with the other ingredients in any order. Mixing may be achieved in a conventional mixer, such as a V-Blender, and is conducted for a period of time sufficient to ensure a substantially uniform mixture of the components.
Thereafter, the powderous mixture is compressed at a pressure ranging from about 200 to about 1600, preferably from about 2~0 to about 650 pounds per square inch, such as with a Carver Press, such that a compressed powder formulation which will maintain its physical integrity upon handling is obtained. Both mixing and compressing should be conducted in the substantial absence of free water which can solubilize the ingredients of the form~ulation which can in turn adversely affect the payout.
The shape of the compressed powder formulation is selected according to the intended use of the formulation.
Depending upon the specific ingredients in the formulation, the compressed powder formulation may be ~ade into antiperspirant or antideodorant sticks which are sized and shaped for convenient .
:~7~Z42 human use, eye shadows, make-up compacts, make-up sticks, blushes or rouge sticks, aftershave sticks, perfume sticks, talcum powder sticks, antisepticidal sticks or pellets, artistic chalks or foot powder sticks. The preferred formulations are used for antiperspirant and deodorant sticks.
In order for the proper amount of material to be obtained by contact with the cornpressed powder formulation, it has a payout ranging from about 10 to about 100 milligrams, preferably from about 40 to about 80 milligrams. Payout is determined by attaching a filter paper (whatman #541) securely to the pan of an electronic balance. Using the test material having the dimensions of a cylinder of 28mm in diameter, the compressed powder formulation is contacted with the surface of the filter paper and pressed down with a force that registers between 50-100 - grams on the balance. The stick is drawn across the filter paper 5 times (3 inches in each draw). The force during the draws should register between 50-100 grams. The "payout" corresponds to the total weight of the product deposited on the filter paper after the 5 drawdowns. Naturally, this test should be repeated several times to ensure that the results are consistent.
To a certain extent, payout can be controlled by regulating the molding pressure. Higher molding pressures generally lead to lower payouts and vice-versa. The payout should additionally be substantially uniform as indicated by an absence of large pieces te.g., greater than one eighth inch in maxim~m dimension) breaking from the formulation. The absence of such large pieces is a further indication that the compressed powder formulcltion will maintain its physical integrity upon handling.
~Z7~7242 An additional benefit of the compressed powder formulation of the present invention is that contact with moisture does not substantially adversely affect its payout property. That is, in contrast to many formulations which tend to exhibit a glazing effect when contacted with moisture, such as may be present in the form of wat:er or perspiration on the skin, the compressed powder formulation of the present invention retains a payout of at least about 90%, preferably at least about 95~ of its original payout. This significant advantage may be determined by immersing the pressed powder formulation in room temperature water for 30 seconds, permitting the formulation to completely dry and then conducting the payout test noted above.
In those instances wherein the compressed powder formulation does not contain a water soluble ingredient such as aluminum chlorohydrate, the formulation apparently regains its payout value by a simple drying mechanism. However, when a water soluble ingredient is present, the formulation regains its payout value by an exfoliation process wherein the surface cracks and peels off as flakes upon drying thereby revealing fresh surface. From an aesthetic standpoint, it is preferred that the flakes be smaller in size such as in the range of from about 1 to about 3 millimeters in maximum dimension.
As used in the present context, the term "consisting essentially of n excludes amounts of materials which will substantially adversely affect the ability of the formulation to be formed into a compressed body or will substantially adversely affect the compressed powder formulation to substantially regain its payout after being contacted with water.
77;~2 The following inventive examples and comparative examples are given to illustrate and contrast the present invention. However, the examples should not be construed as limiting the invention. Unless otherwise indicated, all percentages are given in weight percent of the total Eormulation.
The Organophilic Clays Various organophilic clays are prepared in accordance with the processes briefly described above and more fully disclosed the U.S. patents- Th~
organophilic clays are all available from NL Chemicals, Inc. of Hightstown, N.J. and have the following designations:
Organophilic Clay A - Bentone 27 Organophilic Clay B - Bentone 34 Organophilic Clay C - Bentone 38 Organophilic Clay D - Bentone SD-l Organophilic Clay E - Bentone SD-2 Screening Tests Organophilic Clays A-E along with conventional '0 materials Thixcin R (which is a wax-type product available from NL Chemicals, Inc.), talc, hydrophobic starch and microcrystalline cellulose are compressed into cylindrical sticks from having the dimensions 28mm in diameter and 20mm in height using a Carver Press at various pressures. Pressure was varied to try and optimize properties be~ore they were tested to determine if they will maintain their physical integrity upon handling (i.e., absence of crumbling under minimal pressures), ~1 ~77242 -- have acceptable payout and will retain an acceptable payout ater being contacted with water. The results are set forth in Table I.
TABLE I
Pressure Physical Effect of (lbs/sq. in) InteqritY Payout Water Organophilic Clay A 650 Good Good Good Organophilic Clay B 650 Gcod ~x~ Gcod Organophilic Clay C 650 Good Gocd Good O Organophilic Clay D 250 Good Good ~x~
Organophilic Clay E . 250 ~x~ ! GoodGood Thixcin R 200 ~x~ No ~x~ ~x~
Talc 1600 No ~x~ Good No Gccd ~ydrophobic starch (1) 1600 No ~x~ Good Gccd Microcrystalline oellulose (2) 500 Good Good No Good . .
(1) "Dry Flo"~available from National Starch ComFany (~) "Avioel pH 101" available from FMC Corporation 0 Compressed Formulations Further quantities of Organophilic Clay A are mixed ` with a variety of types and amounts of conventional additives and the substantially uniform mixture of the ingredients are pressed into a cylindrical stick form having a 28mm diameter and 20mm height using a Carver Press at a pressure of 650 pounds per square inch. The resulting sticks are tested to determine if an acceptable payout is maintained after contact with water and the results are set forth in Table II.
.
~?
~ Z7724;~:
TABLE II
A~itive Payout After ditive F~mction water Contact 25~ Aluminum Chlorohydrate Antiperspirant Acceptable 20~ Aluminum Chlorohydrate Antiperspirant Acceptable 10~ Aluminum Chlorohydrate De~rant Borderline 5~ Aluminum Chlorohydrate Deodorant Not Acceptable 20% Al~minum Zirconium Antiperspirant ! Acceptable Tetrachlorohydrex-Gly 0.1~ Benzethonium Chloride Deo~orant Acceptable 0.1~ Triclosan Deodorant Acceptable 2% I~IXCIN R Deodorant Not Acceptable 1~ Magnesium Stearate Lubricating Agent Acceptable 10~ Talc Filler Acceptable 25~ Talc Filler Acceptable 50~ Talc Filler Aoceptable 100~ Talc Filler Not Acceptable To illustrate the use of combinations of additives several formulations are prepared using Organophilic Clay A
compressed into cylindrical sticks having 28mm in diameter and 20mm height by a Carver Press at a preQsure of 650 pounds per squa~re inch and are tested for physical integrity, payout and payout after contact with water. The formulations and the results are se~ forth below.
Formulation 1 Organophilic Clay A 79~ Acceptable Aluminum Chlorohydrate 20%
Magnesium Stearate 1 .
. .
~;~7~7Z~
Formulation 2 Organophilic Clay A 75~ Payout Aluminum Chlorohydrate20~ Not Acceptable Stearic Acid 5%
Formulation 3 Organophilic Clay A 30% Very Brittle Aluminum Chlorohydrate 20~
Hydrophobic Starch (1)50%
Formulation 4 Organophilic Clay A 40~ Acceptable Aluminum Chlorohydrate 20 Talc Formulation 5 Organophilic Clay A 99.9% Acceptable Benzethonium Chloride 0.1%
Formulation 6 Organophilic Clay A 20% Acceptable Aluminum Chlorohydrate20%
Talc 60%
Formulation 7 - Organophilic Clay A 75% Acceptable Aluminum Chlorohydrate25%
Formulation 8 : Organophilic Clay A 80% Acceptable Aluminum Zirconium Chlorohydrex 20 Formulation 9 Organophilic Clay A 50% Acceptable Aluminum Chlorohydrate20%
Microcrystalline Cellulose (2) 30 (1) "Dry Flo" available from --National Starch Company.
(2) "Avicel PH 101" available from FMC Corpora'ion.
The invention being thus described, it will be obvious ; that the same may be varied in many ways~ such variations are not to be regarded as a departure from the spirit and scope of the 9.277Z42 invention, and all such modifications are intended to be included within the scope of the following claims.
.
where 0.58 -x -1~18, 0 -y - 0.66, f - 4 and R is selected from the group consisting oE Na, Li, NH4, and mixtures thereof;
Stevensite - [( 96-x)sigo2o(oH)4-f~Ff]2xR~
where 0.28 'x '0.57, f = 4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof.
These clays may be synthesiæed hydrothermally by forming an aqueous reaction mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as the case may be, sodium (or alternate exchangeable cation or mixture thereof) fluoride in the proportions defined by the above formulas and the preselected values of x, y and f for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approximately 100 to 325~C., preferably 275 to 300C., for a suf~icient period of time to form the desired product.
Formulation times of 3 to 48 hours are typical at 300C.
depending on the particular smectite-type clay being synthesized, and the optimum time can readily be determined by pilot trials.
Representative hydrothermal processes for preparing synthetic smectite clays are described in U.S. Patent Nos. 3,252,757 "
~ IL277X~X
~,586,478, 3,666,407, 3,671,190, 3,844,g78, 3,844,979, 3,852,405 and 3,855,147.
The cation exchange capacity of the smectite clay can be determined by the well-known ammonium acetate method.
The organic cation which is reacted with this smectite-type clay is preferably an ammonium cation which contains at least one lineal or branched, saturated or unsaturated alkyl ~roup having 12 to 22 carbon atoms. The remaining groups of the ammonium cation are chosen from (a) lineal or branched alkyl groups having 1 to 22 carbon atoms; (b) aralkyl groups which are ben~yl and substituted benzyl moieties including fused ring moieties having lineal or branched 1 to 22 carbon atoms in the alkyl portion of the structure; (c) aryl groups such as phenyl and substituted phenyl including fused ring aromatic substituents; (d) beta, gamma, unsaturated groups having six or less carbon atoms or hydroxyalkyl groups having two to six carbon atoms; and (e) hydrogen.
The long chain alkyl radicals may be derived from natural occurring oils including various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils or fats such as tallow oil. The alkyl radicals may likewise be petrochemically derived such as from alpha olefins.
Representative examples of useful branched, satura~ed radicals include 12-methylstearyl; and 12-ethylstearyl.
Representative examples of useful branched, unsaturated radicals include 12-methyloleyl and 12-ethyloleyl. Representative examples of unbranched satura~ed radicals include lauryl;
stearyl; tridecyl; myristyl (tetradecyl); pentadecyl; hexadecyl;
. ~ i. ., ~, 12772a~2 hydrogenated tallow, docosonyl. Representative examples of unbranched, unsaturated and unsubstituted radicals include oleyl, linoleyl, linolenyl, soya and tallow.
Additional examples of aralkyl, that is benzyl and substituted benzyl moieties would include those materials derived from, e.g. benzyl halides, ben~hydryl halides, trityl halides, ~-halo- ~-phenylalkanes wherein the alkyl chain has from 1 to 22 carbon atoms such as l-halo-l-phenylethane, l-halo~l-phenyl propane, and l-halo-l-phenyloctadecane; substltuted benzyl moieties such as would be derived from ortho, meta and parachlorobenzyl halides, para-methoxybenzyl halides, ortho, meta and para-nitrilobenzyl halides, and ortho, meta and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 22 carbon atoms; and fused ring benzyl-type moieties such as would be derived from 2-halomethylnaphthalene, 9-halomethylanthracene and 9-halomethylphenanthrene, wherein the halo group would be definea as chloro, bromo, iodo, or any other such group which serves as a leaving group in the nucleophilic attack or the benzyl type moiety such that the nucleophile replaces the leaving group on the ben~yl type moiety.
Examples of aryl groups would include phenyl such as in N-alkyl and N,N-dialkyl anilines, wherein the alkyl groups contain between 1 and 22 carbon atoms; ortho, meta and para-nit.rophenyl, ortho, metal and para-alkyl phenyl, wherein the alkyl group contains between 1 and 22 carbon atoms, 2-, 3-, and 4-halophenyl ~herein the halo group is defined as chloro, bromo, : or iodo, and 2-, 3-, and 4-carboxyphenyl and esters thereof, where the alcohol of the ester is derived from an alkyl alcohol, wherein the alkyl group contains between 1 and 22 carbon atoms, _g_ ~.2'77Z4~:
aryl such as a phenol, or aralkyl such as benzyl alcohols; fused ring aryl moieties such as naphthalene, anthracene, and phenarthene.
The ~,y -unsaturated alkyl group may be selected from a wide range of materials. These compounds may be cyclic or acyclic, unsubstituted or substituted with aliphatic radicals containing up to 3 carbon atoms such that the total number of aliphatic carbons in the ~,Y-unsaturated radical is 6 or less.
The ~ unsaturated alkyl radical may be substituted with an aromatic ring that likewise is conjugated with Ithe unsaturation of the ~,y moiety or the ~,y-radical is substituted with both aliphatic radicals and aromatic rings.
Representative examples of cyclic ~,y -unsaturated alkyl ~roups include 2-cyclohexenyl and 2-cyclopentenyl.
Representative examples of acyclic ~,y -unsaturated alkyl groups containing 6 or less carbon atoms include propargyl; allyl(2-propenyl); crotyl(2~butenyl); 2-pentenyl 2-hexenyl; 3-methyl-2-butenyl; 3-methyl-2-pentenyl; 2,3-dimethyl-2-butenyl; 1,1-dimethyl-2-propenyl; 1,2-dimethyl propenyl; 2,4-pentadienyl; and 2,4-hexadienyl. Representative examples of acyclic-aromatic substituted compounds include cinnamyl(3-phenyl-2-propenyl);
2-phenyl-2-propenyl; and 3-(4 methoxyphenyl)-2-propenyl.
Representative examples of aromatic and aliphatic substituted materials include 3-phenyl-2-cyclohexenyl; 3 phenyl-2-cyclopentenyl; l,l-dimethyl-3-phenyl-2-propenyl; 1,1,2-trimethyl-3-phenyl-2-propenyl; 2,3-dimethyl-3-phenyl-2-propenyl; 3,3-dimethyl-2-phenyl-2-propenyl and 3-phenyl-2-butenyl.
The hydroxyalkyl group is selected from a hydroxyl substituted aliphatic radical wherein the hydroxyl is not ~L27~42 substituted at the carbon adjacent to the positively charged atom, and the group has from 2 to 6 aliphatic carbons. The alkyl group may be substituted with an aromatic ring independently from the 2 to 6 aliphatic carbons. Representative examples include 2-hydroxyethyl (ethanol); 3~hydroxypropyl; 4-hydroxypentyl; 6-hydroxyhexyl; 2-hydroxypropyl (isopropanol); 2-hydroxybutyl; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclohexyl; 3-hydroxy-cyclohexyl; 4-hydroxycyclohexyl; 2-hyclroxycyclopentyl; 3-hydroxycyclopentyl; 2-methyl-2-hydroxypropyl; 1,1,2-trimethyl-2-hydroxypropyl; 2-phenyl-2-hydroxyethyl; 3-methyl-2-h~droxybutyl;
and S-hydroxy-2 pentenyl.
The organic cation can thus be considered as having the following formula:
r 1 1 1 ~2 - I - R4 wherein Rl is the long chain alkyl group and R2, R3 and R4 are representative of the other possible groups described above.
The preferred organic cation is where Rl is hydrogenated tallow, R2 is benzyl and R3 and R4 are methyl.
Organophilic clay prepared from this organic cation is more fully described in U.S. Patent 4,116,866 which is commercially available from NL Chemicals, Inc.
under the trademark Bentone 27.
The amount of organic cation reacted with the smectite-type clay depends upon the specific clay and the desired degree of hydrophobicity. Typically, the amount of cation ranges from .f~ ' about 90 to about 150, preferably from about 95 to about 120 milliequivalents per 100 grams of clay, 100~ active basis.
The anion which will normally accompany the organic cation is typically one which will not adversely affect the reaction product or the recovery of the same. Such anions may be exemplified by chloride, bromide, iodide, hydroxyl, nitrite and acetate in amounts sufficient to neutralize the organic cation.
The preparation of the organic cationic salt (i.e., the organic cation paired with the anion) and the organophilic clay can be achieved by techniques well known in the!art. For example, when preparing a quaternary ammonium salt, one skilled in the art would prepare a dialkyl secondary amine, for example, by the hydrogenation of nitriles, see u.S. Patent No. 2,355,356, and then form the methyl dialkyl tertiary amine by reductive alkylation using formaldehyde as a source of the ~ethyl radical. According to procedures set forth in U.S. Patent No.
3,136,819 and U.S. Patent No. 2,775,617, quaternary amine halide may then be formed by adding benzyl chloeide or benzyl bromide to the tertiary amine. The contents of these three patents are 20 hereby incorporated by reference. As is well known in the art, the reaction with benzyl chloride or benzyl bromide can be completed by adding a minor amount of methylene chloride to the reaction mixture so that a blend of products which are predominantly benzyl substituted is obtained. This blend may then be used without further separation o~ components to prepare the organophilic clay.
The organophilic clays can be prepared by admixing the clay, the organic cationic salt and water together, preferably at a temperature within the range from about 20 to about lOO~C., ar~d pre~erably from about 35 to about 77C. for a period of time sufficient for the organic compound to coat the clay particles.
Thereafter, the organophilic clay can be subjected to a variety of optional recovery steps such as filtering, washing, drying and grinding.
Illustrative of the numerous patents which describe organic cationic salts, their manner o,E preparation and their use in the preparation of organophilic clays are commonly assigned United States Patent Nos. 2,96S,506, 4,105,578, 4,116,866, 4,208,218, 4,391,637, 4,434,076 and 4,450,095.
The organophilic clay used in the present invention may also be the reaction product of the smectite-type clay, the organic cation and an organic anion. The organic anion is selected from a wide range o materials which are capable of reacting with the organic cation in order to form an organic cation/organic anion complex which may be intercalated with the smectite-type clay. The molecular weight (gram molecular weight) of the organic anion is preferably 3,000 or less, and most preferably 1,000 or less and contains at least one acidic moiety per molecule so as to permit the formation of the organic cation/organic anion complex. The organic anion is preferably derived from an organic compound having a pKA less than about 11Ø
Preferable organic anions are derived from carboxylic acid, such as benzoic acid, sulfonic acids and alkyl sulfates, such as the lauryl half ester of sulfuric acid.
The organic anion, which includes mixtures of organic anions, is reacted with the organic cation and smectite-type clay ~ ,,27t~2~2 o form the organophilic clay and may be added to the reaction mixture in acid or salt form. Exemplary of the latter form are alkali metal salts, alkaline earth salts, ammonia and organic amines.
The amount of organic anion eeacted with smectite-type clay and the organic cation typically ranges from about 5 to about 100 milliequivalents, preferab.ly from about 10 to about 50 milliequivalents per 100 grams of clay, 100% active basis.
Illustrative patents which describe suitable organic anions which may be co-reacted with the organic cation and the smectite-type clay in order to form the organophilic clay include commonly assigned U.S. Patent Nos. 4,412,018 and 4,434,075.
The topical agent used in the compressed powder formulation may be any one or combination of materials commonly applied to a surface, especially the surface of skin. Exemplary topical agents are antiperspirant agents, deodorant agents, pigments, antifungal agents and insect repellants. The formulation may also include conventional fillers and/or processing aids, such as lubricating a~ents. Of course, the specific ingredient or ingredients used in the compressed powder formulation are selected depending upon the desired end use of the formulation. For example, when the compressed powder formulation is designed to have antiperspirant characteristics, the formulation may contain from about 10 to about 30%, preferably about 15 to about 25% by weight of known antiperspirant agents such as aluminum, chlorohydrate, aluminum chlorohydrex, aluminum zirconium chlorohydrate, aluminum ~;2772~Z
zirconium chlorohydrex, aluminum zirconium glycine complexes and mixtures thereof. The preferred antiperspirant agent is aluminum chlorohydrate.
The deodorant agent may be used alone or in combination with the antiperspirant agent and may be present in an amount ranging from about 0.05 to about 10~, preferably from about 0.1 to about 1% by weight. Typical deodorant agents include benzethonium chloride, triclosan, aluminum chlorohydrate, aluminum zirconium chlorohydrate, sodium aluminum chlorhydroxy lactate, cetyl pyridinium chloride, fragrances which will mask odors and mixtures thereof. The preferred deodorant agents are benzethonium chloride and triclosan.
Pigments which may be present in the compressed powder formulation may be any of those known in the art which do not substantially adversely affect the desired characteristics of the formulation. Fxemplary pigments are ultramarine blue, chromium oxide green, black iron oxides, titanium dioxides and mixtures thereof. When present, the amount of pigment is from about 0.5 to about 30%, preferably from about 3 to about 15% by weight.
Antifungal agent may be present in the compressed powder formulation in an amount ranging from about 1 to about 10%, preferably from about 3 to about 5~ by weight. Exemplary antifungal agents include zinc undecylenate, undecylenic acid and mixt~ures thereof. The preferred antifungal agent is a mixture of ~inc undecylenate and undecylenic acid.
Filler may be present in the compressed powder formulation in order to dilute the concentration of the active ingredients or reduce the cost. Typical fillers include talc, dicalcium phosphate, hydrophobic starch, microcrystalline ~77Z42 cellulose and mixtures thereof with the preferred filler being talc. When present, the amount of filler is fro~ about 5 to about 60~, preferably from about 20 to about 40% by weight.
A lubricating agent is used in the compressed powder formulation for the purpose of facilitating the release of the formulation from the compression mold. Typical lubricating agents include magnesium stearate, stearic acid, zinc stearate, calcium stearate and mixtures thereof with the preferred lubricating agent being magnesium stearate. When present, the amount of lubricating agent is from about 0.5 to about 3%r preferably from about 1 to about 2~ by weight.
The compressed powder formulation may be prepared by mixing the organophilic clay with the other ingredients in any order. Mixing may be achieved in a conventional mixer, such as a V-Blender, and is conducted for a period of time sufficient to ensure a substantially uniform mixture of the components.
Thereafter, the powderous mixture is compressed at a pressure ranging from about 200 to about 1600, preferably from about 2~0 to about 650 pounds per square inch, such as with a Carver Press, such that a compressed powder formulation which will maintain its physical integrity upon handling is obtained. Both mixing and compressing should be conducted in the substantial absence of free water which can solubilize the ingredients of the form~ulation which can in turn adversely affect the payout.
The shape of the compressed powder formulation is selected according to the intended use of the formulation.
Depending upon the specific ingredients in the formulation, the compressed powder formulation may be ~ade into antiperspirant or antideodorant sticks which are sized and shaped for convenient .
:~7~Z42 human use, eye shadows, make-up compacts, make-up sticks, blushes or rouge sticks, aftershave sticks, perfume sticks, talcum powder sticks, antisepticidal sticks or pellets, artistic chalks or foot powder sticks. The preferred formulations are used for antiperspirant and deodorant sticks.
In order for the proper amount of material to be obtained by contact with the cornpressed powder formulation, it has a payout ranging from about 10 to about 100 milligrams, preferably from about 40 to about 80 milligrams. Payout is determined by attaching a filter paper (whatman #541) securely to the pan of an electronic balance. Using the test material having the dimensions of a cylinder of 28mm in diameter, the compressed powder formulation is contacted with the surface of the filter paper and pressed down with a force that registers between 50-100 - grams on the balance. The stick is drawn across the filter paper 5 times (3 inches in each draw). The force during the draws should register between 50-100 grams. The "payout" corresponds to the total weight of the product deposited on the filter paper after the 5 drawdowns. Naturally, this test should be repeated several times to ensure that the results are consistent.
To a certain extent, payout can be controlled by regulating the molding pressure. Higher molding pressures generally lead to lower payouts and vice-versa. The payout should additionally be substantially uniform as indicated by an absence of large pieces te.g., greater than one eighth inch in maxim~m dimension) breaking from the formulation. The absence of such large pieces is a further indication that the compressed powder formulcltion will maintain its physical integrity upon handling.
~Z7~7242 An additional benefit of the compressed powder formulation of the present invention is that contact with moisture does not substantially adversely affect its payout property. That is, in contrast to many formulations which tend to exhibit a glazing effect when contacted with moisture, such as may be present in the form of wat:er or perspiration on the skin, the compressed powder formulation of the present invention retains a payout of at least about 90%, preferably at least about 95~ of its original payout. This significant advantage may be determined by immersing the pressed powder formulation in room temperature water for 30 seconds, permitting the formulation to completely dry and then conducting the payout test noted above.
In those instances wherein the compressed powder formulation does not contain a water soluble ingredient such as aluminum chlorohydrate, the formulation apparently regains its payout value by a simple drying mechanism. However, when a water soluble ingredient is present, the formulation regains its payout value by an exfoliation process wherein the surface cracks and peels off as flakes upon drying thereby revealing fresh surface. From an aesthetic standpoint, it is preferred that the flakes be smaller in size such as in the range of from about 1 to about 3 millimeters in maximum dimension.
As used in the present context, the term "consisting essentially of n excludes amounts of materials which will substantially adversely affect the ability of the formulation to be formed into a compressed body or will substantially adversely affect the compressed powder formulation to substantially regain its payout after being contacted with water.
77;~2 The following inventive examples and comparative examples are given to illustrate and contrast the present invention. However, the examples should not be construed as limiting the invention. Unless otherwise indicated, all percentages are given in weight percent of the total Eormulation.
The Organophilic Clays Various organophilic clays are prepared in accordance with the processes briefly described above and more fully disclosed the U.S. patents- Th~
organophilic clays are all available from NL Chemicals, Inc. of Hightstown, N.J. and have the following designations:
Organophilic Clay A - Bentone 27 Organophilic Clay B - Bentone 34 Organophilic Clay C - Bentone 38 Organophilic Clay D - Bentone SD-l Organophilic Clay E - Bentone SD-2 Screening Tests Organophilic Clays A-E along with conventional '0 materials Thixcin R (which is a wax-type product available from NL Chemicals, Inc.), talc, hydrophobic starch and microcrystalline cellulose are compressed into cylindrical sticks from having the dimensions 28mm in diameter and 20mm in height using a Carver Press at various pressures. Pressure was varied to try and optimize properties be~ore they were tested to determine if they will maintain their physical integrity upon handling (i.e., absence of crumbling under minimal pressures), ~1 ~77242 -- have acceptable payout and will retain an acceptable payout ater being contacted with water. The results are set forth in Table I.
TABLE I
Pressure Physical Effect of (lbs/sq. in) InteqritY Payout Water Organophilic Clay A 650 Good Good Good Organophilic Clay B 650 Gcod ~x~ Gcod Organophilic Clay C 650 Good Gocd Good O Organophilic Clay D 250 Good Good ~x~
Organophilic Clay E . 250 ~x~ ! GoodGood Thixcin R 200 ~x~ No ~x~ ~x~
Talc 1600 No ~x~ Good No Gccd ~ydrophobic starch (1) 1600 No ~x~ Good Gccd Microcrystalline oellulose (2) 500 Good Good No Good . .
(1) "Dry Flo"~available from National Starch ComFany (~) "Avioel pH 101" available from FMC Corporation 0 Compressed Formulations Further quantities of Organophilic Clay A are mixed ` with a variety of types and amounts of conventional additives and the substantially uniform mixture of the ingredients are pressed into a cylindrical stick form having a 28mm diameter and 20mm height using a Carver Press at a pressure of 650 pounds per square inch. The resulting sticks are tested to determine if an acceptable payout is maintained after contact with water and the results are set forth in Table II.
.
~?
~ Z7724;~:
TABLE II
A~itive Payout After ditive F~mction water Contact 25~ Aluminum Chlorohydrate Antiperspirant Acceptable 20~ Aluminum Chlorohydrate Antiperspirant Acceptable 10~ Aluminum Chlorohydrate De~rant Borderline 5~ Aluminum Chlorohydrate Deodorant Not Acceptable 20% Al~minum Zirconium Antiperspirant ! Acceptable Tetrachlorohydrex-Gly 0.1~ Benzethonium Chloride Deo~orant Acceptable 0.1~ Triclosan Deodorant Acceptable 2% I~IXCIN R Deodorant Not Acceptable 1~ Magnesium Stearate Lubricating Agent Acceptable 10~ Talc Filler Acceptable 25~ Talc Filler Acceptable 50~ Talc Filler Aoceptable 100~ Talc Filler Not Acceptable To illustrate the use of combinations of additives several formulations are prepared using Organophilic Clay A
compressed into cylindrical sticks having 28mm in diameter and 20mm height by a Carver Press at a preQsure of 650 pounds per squa~re inch and are tested for physical integrity, payout and payout after contact with water. The formulations and the results are se~ forth below.
Formulation 1 Organophilic Clay A 79~ Acceptable Aluminum Chlorohydrate 20%
Magnesium Stearate 1 .
. .
~;~7~7Z~
Formulation 2 Organophilic Clay A 75~ Payout Aluminum Chlorohydrate20~ Not Acceptable Stearic Acid 5%
Formulation 3 Organophilic Clay A 30% Very Brittle Aluminum Chlorohydrate 20~
Hydrophobic Starch (1)50%
Formulation 4 Organophilic Clay A 40~ Acceptable Aluminum Chlorohydrate 20 Talc Formulation 5 Organophilic Clay A 99.9% Acceptable Benzethonium Chloride 0.1%
Formulation 6 Organophilic Clay A 20% Acceptable Aluminum Chlorohydrate20%
Talc 60%
Formulation 7 - Organophilic Clay A 75% Acceptable Aluminum Chlorohydrate25%
Formulation 8 : Organophilic Clay A 80% Acceptable Aluminum Zirconium Chlorohydrex 20 Formulation 9 Organophilic Clay A 50% Acceptable Aluminum Chlorohydrate20%
Microcrystalline Cellulose (2) 30 (1) "Dry Flo" available from --National Starch Company.
(2) "Avicel PH 101" available from FMC Corpora'ion.
The invention being thus described, it will be obvious ; that the same may be varied in many ways~ such variations are not to be regarded as a departure from the spirit and scope of the 9.277Z42 invention, and all such modifications are intended to be included within the scope of the following claims.
.
Claims (28)
1. A compressed powder formulation consisting essentially of:
a) from about 10 to about 99.95% by weight of an organophilic clay; and b) from about 0.05% to about 90% by weight of at least one topical agent, wherein the compressed powder formulation maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90% of its original payout after being contacted with water.
a) from about 10 to about 99.95% by weight of an organophilic clay; and b) from about 0.05% to about 90% by weight of at least one topical agent, wherein the compressed powder formulation maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90% of its original payout after being contacted with water.
2. The compressed powder formulation of claim 1 wherein the topical agent is selected from the group consisting of antiperspirant agents, deodorant agents, pigments, antifungal agents, insect repellants and mixtures thereof.
3. The compressed powder formulation of claim 2 wherein the formulation contains from about 10 to about 30% by weight of antiperspirant agent.
4. The compressed powder formulation of claim 3 wherein the antiperspirant agent is selected from the group consisting of aluminum chlorohydrate, aluminum chlorohydrex, aluminum zirconium chlorohydrate, aluminum zirconium chlorohydrex, aluminum zirconium glycine complexes and mixtures thereof.
5. The compressed powder formulation of claim 4 wherein the antiperspirant agent is aluminum chlorohydrate.
6. The compressed powder formulation of claim 5 wherein the formulation is in the form of a stick adapted for human use.
7. The compressed powder formulation of claim 4 wherein the formulation contains from about 15 to about 25% by weight of the antiperspirant agent.
8. The compressed powder formulation of claim 1 wherein the formulation contains from about 0.05 to about 10% by weight of deodorant agent.
9. The compressed powder formulation of claim 8 wherein the deodorant agent is selected from the group consisting of triclosan, benzethonium chloride, aluminum chlorohydrate, aluminum zirconium chlorohydrate, fragrance, sodium aluminum chlorohydroxy lactate, cetyl pyridinium chloride, and mixtures thereof.
10. The compressed powder formulation of claim 9 wherein the deodorant agent is triclosan or benzethonium chloride in an amount ranging from about 0.1 to about 1% by weight.
11. The compressed powder formulation of claim 1 wherein the organophilic clay is the reaction product of a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of clay and at least one organic cation having the formula wherein R1 is an alkyl group containing from 12 to 22 carbon atoms, R2 is a benzyl group and R3 and R4 are methyl groups.
12. The compressed powder formulation of claim 11 wherein the smectite-type clay is bentonite or hectorite.
13. The compressed powder formulation of claim 12 wherein the smectite-type clay is hectorite.
14. The compressed powder formulation of claim 11 wherein from about 90 to about 150 milliequivalents of the cation are reacted with each 100 grams of the smectite-type clay.
15. The compressed powder formulation of claim 11 wherein from about 5 to about 100 milliequivalents of an organic anion derived from an organic compound having a pKA less than about 11.0 is reacted the organic cation and each 100 grams of the smectite-type clay.
16. The compressed powder formulation of claim 15 wherein the organic anion is a mixture of different organic anions.
17. The compressed powder formulation of claim 15 wherein the amount of organic anion ranges from about 10 to about 50 milliequivalents per 100 grams of the smectite-type clay.
18. The compressed powder formulation of claim 1 wherein the payout is in the range of from about 40 to about 80 milligrams.
19. The compressed powder formulation of claim 18 wherein the formulation retains a payout of at least about 95 after being contacted with water.
20. The compressed powder formulation of claim 1 wherein the formulation further comprises at least one of a filler and a lubricating agent.
21. A process for making a compressed powder formulation comprising:
a) mixing from about 10 to about 99.95% by weight of an organophilic clay and from about 0.05 to about 90% of at least one topical agent to obtain a substantially uniform powderous mixture; and b) compressing the powderous mixture at a pressure in the range of from about 200 to about 1600 pounds per square inch to obtain a compressed powder formulation which maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90% of its original payout after being contacted with water.
a) mixing from about 10 to about 99.95% by weight of an organophilic clay and from about 0.05 to about 90% of at least one topical agent to obtain a substantially uniform powderous mixture; and b) compressing the powderous mixture at a pressure in the range of from about 200 to about 1600 pounds per square inch to obtain a compressed powder formulation which maintains its physical integrity upon handling, has a payout of from about 10 to about 100 milligrams and retains at least about 90% of its original payout after being contacted with water.
22. The process of claim 21 wherein the formulation is compressed into the form of a stick adapted for human use.
23. The process of claim 21 wherein the formulation is compressed at a pressure in the range of from about 250 to about 650 pounds per square inch.
24. The process of claim 21 wherein the formulation is prepared in the substantial absence of free water.
25. The process of claim 21 wherein the topical agent is selected from the group consisting of antiperspirant agents, deodorant agents, pigments, antifungal agents, insect repellants and mixtures thereof.
26. The process of claim 25 wherein the formulation contains from about 10 to about 30% by weight of an antiperspirant agent.
27. The process of claim 26 wherein the antiperspirant agent is aluminim chlorohydrate.
28. The process of claim 27 wherein the formulation has a payout of from about 40 to about 80 milligrams.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/713,897 US4659571A (en) | 1985-03-20 | 1985-03-20 | Compressed powder formulation containing organophilic clay and a process for making the formulation |
| US713,897 | 1985-03-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1277242C true CA1277242C (en) | 1990-12-04 |
Family
ID=24867985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000504475A Expired - Fee Related CA1277242C (en) | 1985-03-20 | 1986-03-19 | Compressed powder formulation containing organophilic clay and a processfor making the formulation |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4659571A (en) |
| EP (1) | EP0203681B1 (en) |
| JP (1) | JPS61257914A (en) |
| AT (1) | ATE63057T1 (en) |
| CA (1) | CA1277242C (en) |
| DE (1) | DE3678994D1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861584A (en) * | 1985-10-07 | 1989-08-29 | United Catalysts, Inc. | Allergen absorbent and blocking aerosol composition |
| US5017361A (en) * | 1985-10-07 | 1991-05-21 | United Catalysts, Inc. | Allergen absorbent and blocking aerosol composition |
| JPS6343665A (en) * | 1986-08-11 | 1988-02-24 | 株式会社資生堂 | Deodorant |
| DE3750576T2 (en) * | 1986-07-24 | 1995-04-27 | Shiseido Co Ltd | SPHERICAL SMALL POWDER, METHOD FOR THE PRODUCTION AND COMPOSITION THAT CONTAINS THIS. |
| US4929644A (en) * | 1986-10-24 | 1990-05-29 | Rheox, Inc. | Thickened organic composition having biocidal activity and an additive for thickening and imparting biocidal activity to an organic composition |
| JP2514373B2 (en) * | 1987-08-19 | 1996-07-10 | 株式会社資生堂 | Cosmetics |
| US4927465A (en) * | 1987-10-19 | 1990-05-22 | J. M. Huber Corporation | Kaolin clays for pitch control |
| US5037508A (en) * | 1987-10-19 | 1991-08-06 | J. M. Huber Corporation | Aluminum chlorohydrate or hydrotalcite treated kaolin clays for pitch control |
| CA1332571C (en) * | 1987-11-20 | 1994-10-18 | Allan Robert Burger | Antiperspirant compositions |
| US5112603A (en) * | 1988-12-30 | 1992-05-12 | Miranol Inc. | Thickening agents for aqueous systems |
| US5000947A (en) * | 1989-05-30 | 1991-03-19 | Moleculon, Inc. | Shaped articles containing liquefiable powders for delivery of cosmetic and other personal care agents |
| US4994264A (en) * | 1989-12-15 | 1991-02-19 | Revlon, Inc. | Press molded cosmetic composition with pay off |
| US5049376A (en) * | 1990-01-26 | 1991-09-17 | Revlon, Inc. | Cosmetic powder bar composition and process for making same |
| DE4009347A1 (en) * | 1990-03-23 | 1991-09-26 | Beiersdorf Ag | DESODRATING COSMETIC AGENTS |
| US5702709A (en) * | 1995-04-18 | 1997-12-30 | Enviroderm Pharmaceuticals, Inc. | Skin allergen and irritant barrier lotion |
| US5597556A (en) * | 1995-04-20 | 1997-01-28 | The Mennen Company | Colored bicarbonate containing solid composition |
| US5869033A (en) * | 1996-04-12 | 1999-02-09 | Enviroderm Pharmaceuticals,Inc. | Method of preventing skin irritation caused by fecal enzymes |
| US5882662A (en) * | 1997-05-09 | 1999-03-16 | Avon Products, Inc. | Cosmetic compositions containing smectite gels |
| JP5346533B2 (en) * | 2008-09-29 | 2013-11-20 | 株式会社マンダム | Powdered solid antiperspirant deodorant |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3227657A (en) * | 1962-09-20 | 1966-01-04 | Minerals & Chem Philipp Corp | Glycol coated attapulgite clay and compositions including the same |
| US3800034A (en) * | 1970-12-28 | 1974-03-26 | Kolman Labor Inc | Method for preparing pressed powder makeup sticks and product produced |
| JPS5021793B2 (en) * | 1972-10-23 | 1975-07-25 | ||
| FR2358139A1 (en) * | 1976-07-16 | 1978-02-10 | Oreal | Compacted, lip make=up powder - contg. fats and/or waxes and applied with applicator |
| FR2394290A1 (en) * | 1977-06-13 | 1979-01-12 | Unilever Nv | Deodorising compsns. not contg. antiperspirants - contg. at least two of hydroxy-aliphatic acids, ester(s) amine(s), diol(s) or unsatd. acid salts |
| US4116866A (en) * | 1977-07-01 | 1978-09-26 | N L Industries, Inc. | Organophilic clay gellant |
| US4440741A (en) * | 1977-10-25 | 1984-04-03 | Colgate-Palmolive Company | Bicarbonate-containing stick deodorant |
| FR2414331A1 (en) * | 1978-01-13 | 1979-08-10 | Unilever Nv | DEODORIZING PRODUCTS FOR SKIN TREATMENT |
| JPS554355A (en) * | 1978-06-27 | 1980-01-12 | Lion Corp | Anhidrotic powder stick |
| JPS5634609A (en) * | 1979-08-31 | 1981-04-06 | Lion Corp | Stick-shaped powder cosmetic |
| EP0028853B2 (en) * | 1979-11-07 | 1988-11-02 | THE PROCTER & GAMBLE COMPANY | Antiperspirant compositions |
| US4431673A (en) * | 1980-05-02 | 1984-02-14 | Revlon, Inc. | Cosmetic compositions |
| JPS5748201A (en) * | 1980-09-08 | 1982-03-19 | Tokyo Shibaura Electric Co | Voltage nonlinear resistor |
| US4391637A (en) * | 1981-10-19 | 1983-07-05 | Nl Industries, Inc. | Rheological additive for non-aqueous fluid systems |
| US4434076A (en) * | 1981-10-19 | 1984-02-28 | Nl Industries, Inc. | Clay cation complexes and their use to increase viscosity of liquid organic systems |
| US4434075A (en) * | 1981-10-19 | 1984-02-28 | Nl Industries, Inc. | Anionically modified organophilic clays and their preparation |
| JPS57109706A (en) * | 1980-12-27 | 1982-07-08 | Lion Corp | Powdery cosmetic of stick shape |
| US4477431A (en) * | 1981-01-14 | 1984-10-16 | The Mennen Company | Cosmetic composition containing high levels of powder |
| PH18181A (en) * | 1981-03-09 | 1985-04-12 | Colgate Palmolive Co | Anhydrous antiperspirant composition |
| US4526780A (en) * | 1981-03-09 | 1985-07-02 | Colgate-Palmolive Company | Anhydrous antiperspirant composition |
| US4425328A (en) * | 1981-12-21 | 1984-01-10 | American Cyanamid Company | Solid antiperspirant stick composition |
| US4517112A (en) * | 1982-02-18 | 1985-05-14 | Nl Industries, Inc. | Modified organophilic clay complexes, their preparation and non-aqueous systems containing them |
| US4609545A (en) * | 1982-11-24 | 1986-09-02 | Schlossman Mitchell L | Compressing aid for compressing powders |
-
1985
- 1985-03-20 US US06/713,897 patent/US4659571A/en not_active Expired - Fee Related
-
1986
- 1986-03-19 JP JP61059663A patent/JPS61257914A/en active Pending
- 1986-03-19 CA CA000504475A patent/CA1277242C/en not_active Expired - Fee Related
- 1986-03-19 DE DE8686302001T patent/DE3678994D1/en not_active Expired - Fee Related
- 1986-03-19 EP EP86302001A patent/EP0203681B1/en not_active Expired - Lifetime
- 1986-03-19 AT AT86302001T patent/ATE63057T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE63057T1 (en) | 1991-05-15 |
| US4659571A (en) | 1987-04-21 |
| EP0203681A1 (en) | 1986-12-03 |
| EP0203681B1 (en) | 1991-05-02 |
| DE3678994D1 (en) | 1991-06-06 |
| JPS61257914A (en) | 1986-11-15 |
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